CN105586548A - Massive iron base amorphous alloy with both high strength and high plasticity and preparation method thereof - Google Patents
Massive iron base amorphous alloy with both high strength and high plasticity and preparation method thereof Download PDFInfo
- Publication number
- CN105586548A CN105586548A CN201610075206.XA CN201610075206A CN105586548A CN 105586548 A CN105586548 A CN 105586548A CN 201610075206 A CN201610075206 A CN 201610075206A CN 105586548 A CN105586548 A CN 105586548A
- Authority
- CN
- China
- Prior art keywords
- alloy
- melting
- based amorphous
- amorphous alloy
- block
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/02—Amorphous alloys with iron as the major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/003—Making ferrous alloys making amorphous alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
- C22C33/06—Making ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2200/00—Crystalline structure
- C22C2200/02—Amorphous
Abstract
The invention belongs to the field of high-performance amorphous alloy materials, and in particular, relates to a massive iron base amorphous alloy with both high strength and high plasticity and a preparation method thereof. The preparation method comprises the following steps: firstly, Fe, Fe3P, a transition element M and Fe2O3 powder are used as raw materials, and are molten by vacuum arc to prepare an intermediate alloy; then, like metal C and the intermediate alloy are mixed, and are molten by vacuum arc to prepare a master alloy; and the master alloy is put in a J-shaped quartz tube for quenching after impurity removal to prepare a round rod type iron base amorphous alloy. The method, disclosed by the invention, can prepare a novel massive iron base amorphous alloy material with both high strength and high room-temperature plasticity.
Description
Technical field
The invention belongs to high-performance amorphous alloy material field, be specifically related to have concurrently high strength and heightBlock Fe-based amorphous alloy of plasticity and preparation method thereof.
Background technology
Fe-based amorphous alloy have high intensity and hardness, good wear-corrosion resistance andThe soft magnet performance more excellent than the silicon steel of current extensive use, and other non-crystaline amorphous metals are raw relativelyProducing cost cheaper, is a kind of structure of new generation and functional material that has future. But andMany bulk amorphous alloys with high room temperature compression plasticity are compared, Fe-based amorphous alloy chamberTemperature plasticity is very little, reaches after elastic limit, and calamitous brittle failure occurs soon, and this greatly limitsIts commercial applications process.
At present, researcher mainly improves block iron by adjusting component and preparation technologyThe temperature-room type plasticity of base noncrystal alloy. Ductile-brittle transiton that there are some researches show block Fe-based amorphous alloy is depositedA critical Poisson's ratio, when making its Poisson's ratio approach 0.32 by reasonable adjustment alloying componentTime, can there is obvious plastic deformation in block Fe-based amorphous alloy; There is afterwards researcher to pass through to adjustIn whole block Fe-based amorphous alloy, the content of Mo, P and B has obtained 0.34 Poisson's ratio, obtainsThe temperature-room type plasticity Fe-Cr-Mo-P-C-B block Fe-based amorphous alloy that is 3.2%; Except compositionAdjust, preparation technology also can exert an influence to block Fe-based amorphous plasticity, and researcher adopts glassThe coated purification technique of glass and water quenching, by Fe40Ni40P14B6Glass forming ability be increased toWhen 1.6mm, find that it has good temperature-room type plasticity, can reach 5.2%.
As mentioned above, although have carried out some research, for how passing through reasonably to becomeDivide design and preparation technology to regulate and control the content of impurity oxygen in Fe-based amorphous alloy, thereby obtainHave the block Fe-based amorphous alloy of excellent mechanical performances, also there is no the report of being correlated with. AndImpurity oxygen may come from the reaction in industrial raw materials, production environment or preparation process etc.Number of ways is the unavoidable material impact that affects material property in large-scale production because ofElement, especially true concerning Fe-based amorphous. Therefore, be necessary very much to further investigate industrial productionMiddle impurity oxygen is for impact and the microcosmic mechanism thereof of block Fe-based amorphous alloy intensity and plasticity and toughness.
Summary of the invention
For the problem of above-mentioned existence, the invention discloses and there is high strength and high-temperature-room type plasticityBlock Fe-based amorphous alloy and preparation method thereof, by vacuum arc melting, removal of impurities process withAnd the technique of these three combinations of quenching in J-shaped quartz ampoule, obtain a series of have concurrently high-strengthThe novel block Fe-based amorphous alloy material of degree and high-ductility; In addition, the present invention mixes by researchThe affect rule of prime element oxygen on block Fe-based amorphous alloy ductility and toughness at room temperature, discovery oxygen contentIncrease can cause the reduction of block Fe-based amorphous alloy ductility and toughness at room temperature.
The present invention is achieved by the following technical solutions:
Have the preparation method of the block Fe-based amorphous alloy of high strength and high-ductility concurrently, described preparationFirst method prepares intermediate alloy through vacuum arc melting, then carbon and described centre is closedGold is put into vacuum arc furnace ignition melting, prepares foundry alloy, and described foundry alloy is carried out to removal of impuritiesAfter processing, put into J-shaped quartz ampoule and quench, prepare block Fe-based amorphous alloy.
Further, the preparation of described intermediate alloy is with Fe, Fe3P, transition element M and Fe2O3Powder is raw material.
Further, described method specifically comprises the following steps:
(1) raw material is prepared: with Fe, C, Fe3P, transition element M and Fe2O3Powder isRaw material, by FeaCbPcMdOeIn the atomic percent of each element be converted into mass percent, according toDescribed mass percent takes respectively above-mentioned raw materials; Wherein: 0≤b≤10,0≤c≤15,0≤d≤20，0≤e≤1.5，a＝100-b-c-d-e；
(2) preparation of intermediate alloy: described Fe in the raw material that step (1) is taken,Fe3P, M and Fe2O3Powder is put into vacuum arc furnace ignition, utilizes argon gas to carry out vacuum arc furnace ignitionClean, under ar gas environment, start melting, the condition of melting is: electric current 100-150A, and moltenRefining time 4-5 minute, completes after melting once, and body of heater to be treated is cooling, carries out melting for the second time,The condition of melting is for the second time with melting condition is identical for the first time, according to the condition weight of melting for the first timeRemelt refining at least 3 times, prepares intermediate alloy;
(3) preparation of foundry alloy
The metalloid C that step (1) is taken and step (2) prepare described inBetween alloy put into together vacuum arc furnace ignition, described intermediate alloy is pressed onto that step (1) takesAbove metalloid C, utilize argon gas to clean vacuum arc furnace ignition, under ar gas environment, openBeginning melting, the condition of melting is: electric current 100-200A, smelting time 4-5 minute, completesAfter melting once, body of heater to be treated is cooling, carries out melting for the second time, the condition of melting for the second time withMelting condition is identical for the first time, repeats melting at least 4 times according to the condition of melting for the first time, systemThe standby foundry alloy that obtains;
(4) the removal of impurities processing of foundry alloy
The described foundry alloy that step (3) is prepared is placed in quartz test tube, then addsB2O3-CaO mixture, by described foundry alloy and described B2O3After-CaO mixture mixesHeat purification, foundry alloy after obtaining purifying, the condition that described heating is purified is: heating is carriedPure temperature is 1250 DEG C, and the heating purification time is at least 4 hours, described B2O3-CaO mixesThing is by anhydrous B2O3After mixing with mass ratio 3:1 with CaO, obtain;
(5) produce J-shaped quartz ampoule
Choose an external diameter 15mm, wall thickness 1mm quartz test tube, will in described quartz test tube, fill hydrogenThe mix acid liquor of fluoric acid and nitric acid, soaks and outwells described mix acid liquor and fill after 15 minutesIonized water, carries out ultrasonic cleaning by described quartz test tube, utilizes the flame envelope homogeneous heating institute of firelockState the bottom of quartz test tube, and constantly rotation makes its thermally equivalent softening, then rapid to partThe bottom of described quartz ampoule is pulled into the fine quartz Guan Bingyong fire that external diameter is 1-3mm in airRifle seals the end mouth of pipe of described fine quartz pipe, obtains J-shaped quartz ampoule, described J-shaped quartzOne end external diameter of pipe is 15mm, and other end external diameter is 1-3mm;
(6) preparation of pole shape Fe-based amorphous alloy
After the described purification that step (4) is prepared, foundry alloy puts into prepared by step (5)In described J-shaped quartz test tube, the vacuum being first evacuated in described J-shaped quartz test tube is5-10Pa, with J-shaped quartz ampoule described in argon cleaning, above-mentioned vacuumizing and argon cleaning J-shaped stoneThe operation of English test tube at least in triplicate, is then poured argon gas control in described J-shaped quartz ampouleThe pressure of making in described J-shaped quartz ampoule is 0.7-1.0MPa, with high temperature furnace to described J-shaped stoneEnglish pipe heats, and after described purification, foundry alloy fully melts, and generates foundry alloy liquation, fastSpeed passes into argon gas in J-shaped quartz ampoule, is controlled at the interior J-shaped quartz ampoule of time range of 1-2sInternal pressure reaches 1.5 × 105Pa, is incubated and immediately described J-shaped quartz ampoule is put into matter after 30 secondsIn the amount mark sodium chloride salt aqueous solution that is 10%, cooling after, before described J-shaped quartz ampouleThe solid shape metal forming in end, is described block Fe-based amorphous alloy.
Further, in step (1), described transition element M be Al, Cu, Ga,Any one in Co, Ni, Cr, Ti, V, Zr, Nb, Ta and Hf.
Further, in step (2) and step (3), the described argon gas that utilizes is to vacuumThe method that electric arc furnaces cleans is specially: being first evacuated to vacuum is 3.0 × 10-3Pa-3.5×10-3Pa, recharges argon gas to pressure 0.1MPa, and then is evacuated to vacuum and is7.5×10-4Pa-8.0×10-4Pa, then recharge argon gas to pressure 0.1MPa.
Have a block Fe-based amorphous alloy for high strength and high-ductility concurrently, according to the described height that has concurrentlyThe preparation method of the block Fe-based amorphous alloy of intensity and high-ductility prepares, and preparesThe chemical formula of described block Fe-based amorphous alloy is FeaCbPcMdOe, wherein: 0≤b≤10,0≤ c≤15,0≤d≤20,0≤e≤1.5, a=100-b-c-d-e, M is transition elementAny one in Al, Cu, Ga, Co, Ni, Cr, Ti, V, Zr, Nb, Ta and Hf.
Further, described block Fe-based amorphous alloy is cylindric, and diameter is0.7mm-2.9mm。
Useful technique effect of the present invention:
(1) block Fe-based amorphous alloy preparing by preparation method disclosed by the inventionThere is high strength and excellent temperature-room type plasticity, when its as cast condition compressive strength can reach 3000MPa withUpper, room temperature fracture plasticity is more than 5%, and high energy reaches 17%, has greatly improved current iron-basedThe ductility and toughness at room temperature of block amorphous alloy.
(2) method of utilizing J-shaped quartz ampoule to prepare Fe-based amorphous alloy is compared traditional copper mold and is inhaledCasting method, owing to having reduced the heterogeneous nucleation effect that melt contacts with copper mold, has reducedNanocrystalline formation, therefore can obtain larger ductility and toughness at room temperature.
(3) block Fe-based amorphous alloy that the preparation method who proposes in the present invention prepares isDiameter is the cylindric full amorphous bar of 1mm at least, and maximum full amorphous coupon diameter can reach2.9mm, detects and confirms all through X ray detection, SEM scanning electron microscope analysis and electronic diffractionFor full non crystalline structure, and this alloy system glass transition point is 630-710K, crystallization start temperatureFor 650-730K.
(4) high-performance block Fe-based amorphous alloy material provided by the invention structural material,Precision optical machinery, Aero-Space etc. are all with a wide range of applications in field.
(5) the present invention moulds tough by research impurity element oxygen to block Fe-based amorphous alloy room temperatureProperty affect rule, it is tough that the increase of finding oxygen content can cause block Fe-based amorphous alloy room temperature to be mouldedThe reduction of property.
Brief description of the drawings
Fig. 1 is the Fe making in embodiment 165C6.5P11.5Ni17And make in embodiment 2Fe64.98C6.5P11.5Ni17O0.02The compressive stress strain curve of cylindric Fe-based amorphous alloy;
Fig. 2 is the Fe making in embodiment 165C6.5P11.5Ni17And make in embodiment 2Fe64.98C6.5P11.5Ni17O0.02The DSC test curve of cylindric Fe-based amorphous alloy;
Fig. 3 is the Fe making in embodiment 264.98C6.5P11.5Ni17O0.02Cylindric block Fe-based non-The exterior appearance of peritectic alloy bar;
Fig. 4 is the Fe making in embodiment 264.98C6.5P11.5Ni17O0.02Cylindric Fe-based amorphous closingGold compression failure trailing flank pattern;
Fig. 5 is the Fe making in embodiment 264.98C6.5P11.5Ni17O0.02Cylindric Fe-based amorphous closingThe pattern of gold high-resolution-ration transmission electric-lens.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction withDrawings and Examples, are explained in further detail the present invention. Should be appreciated that this place retouchesThe specific embodiment of stating only, for explaining the present invention, is not intended to limit the present invention.
On the contrary, the present invention contain any defined by claim in marrow of the present invention and scopeOn make substitute, amendment, equivalent method and scheme. Further, in order to make the public to thisBright having a better understanding, in below details of the present invention being described, has detailedly described some spiesFixed detail section. Do not have for a person skilled in the art the description of these detail sections can yetTo understand the present invention completely.
Embodiment 1
Have the preparation method of the block Fe-based amorphous alloy of high strength and high-ductility concurrently, described preparationFirst method prepares intermediate alloy through vacuum arc melting, then carbon and described centre is closedGold is put into vacuum arc furnace ignition melting, prepares foundry alloy, and described foundry alloy is carried out to removal of impuritiesAfter processing, put into J-shaped quartz ampoule and quench, prepare block Fe-based amorphous alloy. ItsIn, the present invention, in the preparation process of foundry alloy, first prepares intermediate alloy, and then by classMetal carbon is put into vacuum arc furnace ignition melting together with described intermediate alloy, prepares mother and closesGold, because the fusing point of metalloid carbon is very high, as directly mixed with other raw material, is difficult to moltenChange, and it is low weight, in the process of preparing foundry alloy, should be noted that intermediate alloy is pressedOn carbon, prevent that electric arc blows away C in the time carrying out melting.
The present embodiment is with Fe65C6.5P11.5Ni17Pole shape non-crystaline amorphous metal be prepared as example:
Preparation method specifically comprises the following steps:
(1) raw material is prepared
With purity all higher than 99.9% Fe, C, Fe3P and Ni are raw material, by Fe65C6.5P11.5Ni17In the atomic percent of each element be converted into mass percent, according to described mass percent respectivelyTake above-mentioned raw materials; Using accuracy is 10-3Gram electronic balance take raw material, its RawFe2O3As the source of element O, by adding the Fe of different content2O3Introduce different contentOxygen.
(2) preparation of intermediate alloy
Described Fe, Fe in the raw material that step (1) is taken3P and Ni put into electrodeless damageIn the vacuum arc furnace ignition of consumption, being first evacuated to vacuum is 3.0 × 10-3Pa, recharges argon gasTo pressure 0.1MPa, and then to be evacuated to vacuum be 7.5 × 10-4Pa, then recharge argon gas extremelyPressure 0.1MPa starts melting under ar gas environment, and the condition of melting is: electric current 150A,Smelting time 5 minutes, completes melting once, the bar of basis melting for the first time after body of heater is coolingPart carries out melting for the second time, at least repeats melting 3 times, prepares intermediate alloy.
(3)Fe65C6.5P11.5Ni17The preparation of foundry alloy
The described intermediate alloy that the C that step (1) is taken and step (2) preparePut into together vacuum arc furnace ignition, easily blown away by electric arc because the density of raw material C is little, soDescribed intermediate alloy must be put into C that step (1) takes above, utilize argon gas to veryEmpty electric arc furnaces cleans, and under ar gas environment, starts melting, and the condition of melting is: electric current200A, smelting time 5 minutes, completes melting once, and after body of heater is cooling, basis is molten for the first timeThe condition of refining is carried out melting for the second time, at least repeats melting 4 times, prepares foundry alloy.
(4)Fe65C6.5P11.5Ni17The removal of impurities processing of foundry alloy
The Fe that step (3) is prepared65C6.5P11.5Ni17Foundry alloy is placed in quartz test tube,Then add B2O3-CaO mixture, by described foundry alloy and described B2O3-CaO mixture is mixedAfter closing evenly, heat purification, foundry alloy after obtaining purifying, the condition that described heating is purified is:Heating purification temperature is 1250 DEG C, and the heating purification time is at least 4 hours, described B2O3-CaOMixture is by anhydrous B2O3After mixing with mass ratio 3:1 with CaO, obtain; Heating purification processIn, B2O3The melting of-CaO mixture forms medium solution, and foundry alloy is by B2O3-CaO mixture is moltenMelt and form the molten parcel of medium, purify for a long time, after purifying, the alloying component of foundry alloy is equalImpurity even and wherein reduces; Simultaneously above-mentioned removal of impurities process can be removed a small amount of in foundry alloyOxygen, can pass through to control removal of impurities process to control oxygen content in foundry alloy, and then can study oxygenThe affect rule of content on block Fe-based amorphous alloy plasticity and toughness.
(5) produce J-shaped quartz ampoule
Choose an external diameter 15mm, wall thickness 1mm quartz test tube, will in described quartz test tube, fill hydrogenThe mix acid liquor of fluoric acid and nitric acid, soaks and outwells described mix acid liquor and fill after 15 minutesIonized water, carries out ultrasonic cleaning by described quartz test tube, utilizes the flame envelope homogeneous heating institute of firelockState the bottom of quartz test tube, and constantly rotation makes its thermally equivalent softening, then rapid to partThe bottom of described quartz ampoule is pulled into the fine quartz Guan Bingyong fire that external diameter is 1-3mm in airRifle seals the end mouth of pipe of described tubule, obtains J-shaped quartz ampoule, described J-shaped quartz ampouleOne end external diameter is 15mm, and other end external diameter is 1-3mm.
(6)Fe65C6.5P11.5Ni17The preparation of bar-shaped Fe-based amorphous alloy
After the described purification that step (4) is prepared, foundry alloy puts into prepared by step (5)In described J-shaped quartz test tube, by triple valve, J-shaped quartz ampoule and mechanical pump are connected to rear extractionVacuum, the vacuum being first evacuated in described J-shaped quartz test tube is 5-10Pa, uses argonJ-shaped quartz ampoule described in gas flushing, above-mentioned vacuumizing and the operation of argon cleaning J-shaped quartz test tubeAt least repeat twice, to guarantee that the oxygen overwhelming majority in J-shaped quartz ampoule is excluded, then toThe pressure that pours argon gas in described J-shaped quartz ampoule and control in described J-shaped quartz ampoule is0.7-1.0MPa, heats heating-up temperature 1250 with high temperature furnace to described J-shaped quartz ampouleDEG C (under this heating-up temperature, can ensure the abundant fusing of foundry alloy in quartz ampoule, simultaneously JShape quartz ampoule is not melted), after described purification, foundry alloy fully melts, and generates foundry alloy moltenLiquid passes into argon gas rapidly in J-shaped quartz ampoule, is controlled at the interior J-shaped of time range of 1-2sQuartz ampoule internal pressure reaches 1.5 × 105Pa, foundry alloy liquation is subject to just can entering after the punching press of argon gasEnter test tube front end fine quartz tube portion, be incubated and immediately described J-shaped quartz ampoule put into after 30 secondsMass fraction be in 10% the sodium chloride salt aqueous solution in, cooling after, at described J-shaped quartz ampouleFront end in form solid shape metal, for bar-shaped, obtain Fe65C6.5P11.5Ni17Bar-shaped iron-based is non-Peritectic alloy. Compared with conventional art, the present invention puts into J-shaped test tube by foundry alloy and quenches,There are following two advantages: one, can control non-crystaline amorphous metal to be prepared by J-shaped test tubeDiameter; Two, the test tube wall of tubule one end of J-shaped test tube is very thin, when quenching, can obtain ratioThereby larger cooling velocity ensures that it obtains noncrystalline state.
The bar-shaped Fe-based amorphous alloy making is intercepted into the cylindric coupon of φ 1 × 2mm, useInstron testing machine for mechanical properties is measured compression performance, and compression speed is 1 × 10-4s-1. ExperimentRecording its room temperature compressed rupture strength is 3050MPa, and plastic deformation is 17%, its compression stress-Strain curve and DSC test curve are as shown in Figure 1 and Figure 2.
Embodiment 2
Fe64.98C6.5P11.5Ni17O0.02The preparation of amorphous bar
Preparation method specifically comprises the following steps:
(1) raw material is prepared
With purity all higher than 99.9% Fe, C, Fe3P and Ni are raw material, willFe64.98C6.5P11.5Ni17O0.02In the atomic percent of each element be converted into mass percent, according to instituteState mass percent and take respectively above-mentioned raw materials; Using accuracy is 10-3Gram electronic balance claimGet raw material, its Raw Fe2O3As the source of element O;
(2) preparation of intermediate alloy
Described Fe, Fe in the raw material that step (1) is taken3P and Ni put into electrodeless damageIn the vacuum arc furnace ignition of consumption, being first evacuated to vacuum is 3.0 × 10-3Pa, recharges argon gasTo pressure 0.1MPa, and then to be evacuated to vacuum be 7.5 × 10-4Pa, then recharge argon gas extremelyPressure 0.1MPa starts melting under ar gas environment, and the condition of melting is: electric current 150A,Smelting time 5 minutes, completes melting once, the bar of basis melting for the first time after body of heater is coolingPart carries out melting for the second time, at least repeats melting 3 times, prepares intermediate alloy;
(3)Fe64.98C6.5P11.5Ni17O0.02The preparation of foundry alloy
The described intermediate alloy that the C that step (1) is taken and step (2) preparePut into together vacuum arc furnace ignition, easily blown away by electric arc because the density of raw material C is little, soDescribed intermediate alloy must be put into C that step (1) takes above, utilize argon gas to veryEmpty electric arc furnaces cleans, and under ar gas environment, starts melting, and the condition of melting is: electric current200A, smelting time 5 minutes, completes melting once, and after body of heater is cooling, basis is molten for the first timeThe condition of refining is carried out melting for the second time, at least repeats melting 4 times, prepares foundry alloy;
(4)Fe64.98C6.5P11.5Ni17O0.02The removal of impurities processing of foundry alloy
The Fe that step (3) is prepared65C6.5P11.5Ni17Foundry alloy is placed in quartz test tube,Then add B2O3-CaO mixture, by described foundry alloy and described B2O3-CaO mixture is mixedAfter closing evenly, heat purification, foundry alloy after obtaining purifying, the condition that described heating is purified is:Heating purification temperature is 1250 DEG C, and the heating purification time is at least 4 hours, described B2O3-CaOMixture is by anhydrous B2O3After mixing with mass ratio 3:1 with CaO, obtain; Heating purification processIn, B2O3The melting of-CaO mixture forms medium solution, and foundry alloy is by B2O3-CaO mixture is moltenMelt and form the molten parcel of medium, purify for a long time, after purifying, the alloying component of foundry alloy is equalImpurity even and wherein reduces;
(5) produce J-shaped quartz ampoule
Choose an external diameter 15mm, wall thickness 1mm quartz test tube, will in described quartz test tube, fill hydrogenThe mix acid liquor of fluoric acid and nitric acid, soaks and outwells described mix acid liquor and fill after 15 minutesIonized water, carries out ultrasonic cleaning by described quartz test tube, utilizes the flame envelope homogeneous heating institute of firelockState the bottom of quartz test tube, and constantly rotation makes its thermally equivalent softening, then rapid to partThe bottom of described quartz ampoule is pulled into the fine quartz Guan Bingyong fire that external diameter is 1-3mm in airRifle seals the end mouth of pipe of described tubule, obtains J-shaped quartz ampoule, described J-shaped quartz ampouleOne end external diameter is 15mm, and other end external diameter is 1-3mm;
(6)Fe64.98C6.5P11.5Ni17O0.02The preparation of bar-shaped Fe-based amorphous alloy
After the described purification that step (4) is prepared, foundry alloy puts into prepared by step (5)In described J-shaped quartz test tube, by triple valve, J-shaped quartz ampoule and mechanical pump are connected to rear extractionVacuum, the vacuum being first evacuated in described J-shaped quartz test tube is 5-10Pa, uses argonJ-shaped quartz ampoule described in gas flushing, above-mentioned vacuumizing and the operation of argon cleaning J-shaped quartz test tubeAt least repeat twice, to guarantee that the oxygen overwhelming majority in J-shaped quartz ampoule is excluded, then toThe pressure that pours argon gas in described J-shaped quartz ampoule and control in described J-shaped quartz ampoule is0.7-1.0MPa, heats heating-up temperature 1250 with high temperature furnace to described J-shaped quartz ampouleDEG C, after described purification, foundry alloy fully melts, and generates foundry alloy liquation, rapidly to J-shaped stoneYing Guanzhong passes into argon gas, and the interior J-shaped quartz ampoule internal pressure of time range that is controlled at 1-2s reaches1.5×105Pa, foundry alloy liquation is subject to just can entering test tube front end fine quartz after the punching press of argon gasTube portion, being incubated and after 30 seconds, immediately described J-shaped quartz ampoule being put into mass fraction is 10%In in the sodium chloride salt aqueous solution, cooling after, what in the front end of described J-shaped quartz ampoule, form consolidatesShape metal, for bar-shaped, obtains Fe64.98C6.5P11.5Ni17O0.02Bar-shaped Fe-based amorphous alloy, Fig. 3For its exterior appearance figure, Fig. 4 is its compression failure trailing flank pattern.
The bar-shaped Fe-based amorphous alloy making is intercepted into the cylindric coupon of φ 1 × 2mm, useInstron testing machine for mechanical properties is measured compression performance, and compression speed is 1 × 10-4s-1. ExperimentRecording its room temperature compressed rupture strength is 3500MPa, and plastic deformation is 10.5%, and its compression shouldAs shown in Figure 1 and Figure 2, embodiment 2 preparations obtain for force-strain curve and DSC test curveThe Fe obtaining64.98C6.5P11.5Ni17O0.02Bar-shaped Fe-based amorphous alloy and embodiment 1 prepareFe65C6.5P11.5Ni17Bar-shaped Fe-based amorphous alloy is compared, Fe64.98C6.5P11.5Ni17O0.02Bar-shaped iron-based is non-Peritectic alloy room temperature compression plasticity decreases, non-in noncrystal substrate after plasticity decline and doped with oxygenInhomogeneity reduction is relevant, as shown in Figure 5, analyzes knownly by high-resolution-ration transmission electric-lens, mixesThe assorted later Fe of oxygen64.98C6.5P11.5Ni17O0.02In Fe-based amorphous matrix, heterogeneity is lower.
Claims (7)
1. have the preparation method of the block Fe-based amorphous alloy of high strength and high-ductility concurrently, its featureBe, first described preparation method prepares intermediate alloy through vacuum arc melting, then willCarbon and described intermediate alloy are put into vacuum arc furnace ignition melting, prepare foundry alloy, described in inciting somebody to actionFoundry alloy carries out putting into J-shaped quartz ampoule after removal of impurities processing and quenches, and prepares block ironBase noncrystal alloy.
2. have according to claim 1 the block Fe-based amorphous alloy of high strength and high-ductility concurrentlyPreparation method, it is characterized in that, the preparation of described intermediate alloy is with Fe, Fe3P, transition groupElement M and Fe2O3Powder is raw material.
3. having according to claim 1 the block Fe-based amorphous of high strength and high-ductility concurrently closesThe preparation method of gold, is characterized in that, described method specifically comprises the following steps:
(1) raw material is prepared: with Fe, C, Fe3P, transition element M and Fe2O3Powder isRaw material, by FeaCbPcMdOeIn the atomic percent of each element be converted into mass percent, according toDescribed mass percent takes respectively above-mentioned raw materials; Wherein: 0≤b≤10,0≤c≤15,0≤d≤20，0≤e≤1.5，a＝100-b-c-d-e；
(2) preparation of intermediate alloy: described Fe in the raw material that step (1) is taken,Fe3P, M and Fe2O3Powder is put into vacuum arc furnace ignition, utilizes argon gas to carry out vacuum arc furnace ignitionClean, under ar gas environment, start melting, the condition of melting is: electric current 100-150A, and moltenRefining time 4-5 minute, completes after melting once, and body of heater to be treated is cooling, carries out melting for the second time,The condition of melting is for the second time with melting condition is identical for the first time, according to the condition weight of melting for the first timeRemelt refining at least 3 times, prepares intermediate alloy;
(3) preparation of foundry alloy
The metalloid C that step (1) is taken and step (2) prepare described inBetween alloy put into together vacuum arc furnace ignition, described intermediate alloy is pressed onto that step (1) takesAbove metalloid C, utilize argon gas to clean vacuum arc furnace ignition, under ar gas environment, openBeginning melting, the condition of melting is: electric current 100-200A, smelting time 4-5 minute, completesAfter melting once, body of heater to be treated is cooling, carries out melting for the second time, the condition of melting for the second time withMelting condition is identical for the first time, repeats melting at least 4 times according to the condition of melting for the first time, systemThe standby foundry alloy that obtains;
(4) the removal of impurities processing of foundry alloy
The described foundry alloy that step (3) is prepared is placed in quartz test tube, then addsB2O3-CaO mixture, by described foundry alloy and described B2O3After-CaO mixture mixesHeat purification, foundry alloy after obtaining purifying, the condition that described heating is purified is: heating is carriedPure temperature is 1250 DEG C, and the heating purification time is at least 4 hours, described B2O3-CaO mixesThing is by anhydrous B2O3After mixing with mass ratio 3:1 with CaO, obtain;
(5) produce J-shaped quartz ampoule
Choose an external diameter 15mm, wall thickness 1mm quartz test tube, will in described quartz test tube, fill hydrogenThe mix acid liquor of fluoric acid and nitric acid, soaks and outwells described mix acid liquor and fill after 15 minutesIonized water, carries out ultrasonic cleaning by described quartz test tube, utilizes the flame envelope homogeneous heating institute of firelockState the bottom of quartz test tube, and constantly rotation makes its thermally equivalent softening, then rapid to partThe bottom of described quartz ampoule is pulled into the fine quartz Guan Bingyong fire that external diameter is 1-3mm in airRifle seals the end mouth of pipe of described fine quartz pipe, obtains J-shaped quartz ampoule, described J-shaped quartzOne end external diameter of pipe is 15mm, and other end external diameter is 1-3mm;
(6) preparation of pole shape Fe-based amorphous alloy
After the described purification that step (4) is prepared, foundry alloy puts into prepared by step (5)In described J-shaped quartz test tube, the vacuum being first evacuated in described J-shaped quartz test tube is5-10Pa, with J-shaped quartz ampoule described in argon cleaning, above-mentioned vacuumizing and argon cleaning J-shaped stoneThe operation of English test tube at least in triplicate, is then poured argon gas control in described J-shaped quartz ampouleThe pressure of making in described J-shaped quartz ampoule is 0.7-1.0MPa, with high temperature furnace to described J-shaped stoneEnglish pipe heats, and after described purification, foundry alloy fully melts, and generates foundry alloy liquation, fastSpeed passes into argon gas in J-shaped quartz ampoule, is controlled at the interior J-shaped quartz ampoule of time range of 1-2sInternal pressure reaches 1.5 × 105Pa, is incubated and immediately described J-shaped quartz ampoule is put into matter after 30 secondsIn the amount mark sodium chloride salt aqueous solution that is 10%, cooling after, before described J-shaped quartz ampouleThe solid shape metal forming in end, is described block Fe-based amorphous alloy.
4. have according to claim 3 the block Fe-based amorphous alloy of high strength and high-ductility concurrentlyPreparation method, in step (1), described transition element M be Al, Cu, Ga, Co,Any one in Ni, Cr, Ti, V, Zr, Nb, Ta and Hf.
5. have according to claim 3 the block Fe-based amorphous alloy of high strength and high-ductility concurrentlyPreparation method, it is characterized in that, in step (2) and step (3), described utilizationThe method that argon gas cleans vacuum arc furnace ignition is specially: being first evacuated to vacuum is3.0×10-3Pa-3.5×10-3Pa, recharges argon gas to pressure 0.1MPa, and then is evacuated toVacuum is 7.5 × 10-4Pa-8.0×10-4Pa, then recharge argon gas to pressure 0.1MPa.
6. have a block Fe-based amorphous alloy for high strength and high-ductility concurrently, according to claimDescribed in one of 1-5, have preparation method's system of the block Fe-based amorphous alloy of high strength and high-ductility concurrentlyStandby acquisition, is characterized in that, the chemical formula of the described block Fe-based amorphous alloy preparing isFeaCbPcMdOe, wherein: 0≤b≤10,0≤c≤15,0≤d≤20,0≤e≤1.5,A=100-b-c-d-e, M be transition element Al, Cu, Ga, Co, Ni, Cr, Ti, V,Any one in Zr, Nb, Ta and Hf.
7. a kind ofly according to claim 6 have the block Fe-based non-of high strength and high-ductility concurrentlyPeritectic alloy, is characterized in that, described block Fe-based amorphous alloy is cylindric, and diameter is0.7mm-2.9mm。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610075206.XA CN105586548B (en) | 2016-02-03 | 2016-02-03 | Have block Fe-based amorphous alloy of high intensity and high-ductility and preparation method thereof concurrently |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610075206.XA CN105586548B (en) | 2016-02-03 | 2016-02-03 | Have block Fe-based amorphous alloy of high intensity and high-ductility and preparation method thereof concurrently |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105586548A true CN105586548A (en) | 2016-05-18 |
| CN105586548B CN105586548B (en) | 2017-07-18 |
Family
ID=55926443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610075206.XA Active CN105586548B (en) | 2016-02-03 | 2016-02-03 | Have block Fe-based amorphous alloy of high intensity and high-ductility and preparation method thereof concurrently |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105586548B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106435407A (en) * | 2016-09-30 | 2017-02-22 | 中国矿业大学 | Preparation method of dumbbell-shaped iron base block metal glass sample |
| CN106676432A (en) * | 2016-11-15 | 2017-05-17 | 北京科技大学 | Low-cost and high-forming-capability large iron-base amorphous alloy and composite material thereof |
| CN106756645A (en) * | 2017-02-28 | 2017-05-31 | 深圳市锆安材料科技有限公司 | A kind of inexpensive Fe-based amorphous alloy part preparation technology and Fe-based amorphous alloy part |
| CN108754198A (en) * | 2018-05-25 | 2018-11-06 | 中国矿业大学 | A kind of preparation method of flexibility block metal glass |
| CN109023161A (en) * | 2018-08-30 | 2018-12-18 | 合肥工业大学 | A kind of Fe-Ni-P-C system amorphous alloy elctro-catalyst and its preparation method and application |
| CN112974775A (en) * | 2021-01-23 | 2021-06-18 | 郑州大学 | Die, device and method for preparing amorphous alloy pipe |
| CN115198209A (en) * | 2021-04-09 | 2022-10-18 | 泰州市新龙翔金属制品有限公司 | Iron-based alloy applied to tooth root implant and preparation process thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102899591A (en) * | 2012-10-24 | 2013-01-30 | 华南理工大学 | High-oxygen-content iron-based amorphous composite powder and preparation method thereof |
| CN103757450A (en) * | 2014-01-24 | 2014-04-30 | 新疆大学 | Preparation method of iron-based bulk amorphous alloy with high saturation magnetization |
-
2016
- 2016-02-03 CN CN201610075206.XA patent/CN105586548B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102899591A (en) * | 2012-10-24 | 2013-01-30 | 华南理工大学 | High-oxygen-content iron-based amorphous composite powder and preparation method thereof |
| CN103757450A (en) * | 2014-01-24 | 2014-04-30 | 新疆大学 | Preparation method of iron-based bulk amorphous alloy with high saturation magnetization |
Non-Patent Citations (2)
| Title |
|---|
| 孙中子: "Fe-Cr-P-C非晶态合金耐蚀性能的研究", 《化学工业与工程》 * |
| 李晋锋: "磁性块体Fe80P13C7非晶态合金的制备及其性能研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106435407A (en) * | 2016-09-30 | 2017-02-22 | 中国矿业大学 | Preparation method of dumbbell-shaped iron base block metal glass sample |
| CN106676432A (en) * | 2016-11-15 | 2017-05-17 | 北京科技大学 | Low-cost and high-forming-capability large iron-base amorphous alloy and composite material thereof |
| CN106756645A (en) * | 2017-02-28 | 2017-05-31 | 深圳市锆安材料科技有限公司 | A kind of inexpensive Fe-based amorphous alloy part preparation technology and Fe-based amorphous alloy part |
| CN106756645B (en) * | 2017-02-28 | 2018-07-24 | 深圳市锆安材料科技有限公司 | A kind of low cost Fe-based amorphous alloy part preparation process and Fe-based amorphous alloy part |
| CN108754198A (en) * | 2018-05-25 | 2018-11-06 | 中国矿业大学 | A kind of preparation method of flexibility block metal glass |
| CN109023161A (en) * | 2018-08-30 | 2018-12-18 | 合肥工业大学 | A kind of Fe-Ni-P-C system amorphous alloy elctro-catalyst and its preparation method and application |
| CN112974775A (en) * | 2021-01-23 | 2021-06-18 | 郑州大学 | Die, device and method for preparing amorphous alloy pipe |
| CN112974775B (en) * | 2021-01-23 | 2022-07-15 | 郑州大学 | Die, device and method for preparing amorphous alloy pipe |
| CN115198209A (en) * | 2021-04-09 | 2022-10-18 | 泰州市新龙翔金属制品有限公司 | Iron-based alloy applied to tooth root implant and preparation process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105586548B (en) | 2017-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105586548A (en) | Massive iron base amorphous alloy with both high strength and high plasticity and preparation method thereof | |
| CN102041461B (en) | Zr-based amorphous alloy and preparation method thereof | |
| CN108842076B (en) | Ni-Co-Cr-Ti-Ta high-entropy eutectic alloy and preparation method thereof | |
| CN105886963A (en) | Amorphous platinum-rich alloys | |
| CN107841673A (en) | A series of Fe Co Cr Ni Al high-entropy alloys and its Technology for Heating Processing | |
| CN101705362A (en) | Electroslag remelting quaternary slag system for preparing high-purity stainless steel | |
| CN102703645B (en) | Process for refining and slagging steel cord | |
| CN101016606A (en) | Magnesium-base massive non-crystalline material and preparing method thereof | |
| CN109576516A (en) | A kind of preparation method of electromagnetic wave shielding copper-iron alloy partitioned wire short route | |
| CN103938132A (en) | Zr-based amorphous alloy having strong glass-forming ability | |
| CN102146550B (en) | Nickel-free zirconium alloy with amorphous structure easily formed by pouring melt copper mould | |
| CN114032434B (en) | Smelting of high corrosion resistant N08120 material and production process of large-caliber seamless pipe | |
| CN100368575C (en) | Magnesium alloy cast into amorphous block with centimeter size | |
| CN101705392A (en) | Toughening ferromagnetic shape memory alloy and preparation method thereof | |
| CN105936987B (en) | A kind of preparation method of aluminium nitride carbon nanotube particulate enhancing aluminum-based alloy material | |
| CN108950308A (en) | A kind of chemical equipment falling liquid film pure nickel pipe and preparation method thereof | |
| CN106244946B (en) | A kind of high-strength plasticity zirconium-base amorphous alloy and preparation method containing molybdenum | |
| CN100360703C (en) | Process for preparing iron base non crystal state alloy by bar material plasma spraying | |
| CN107779790B (en) | Germanic no without phosphorus large scale palladium base amorphous alloy of nickel of one kind and preparation method thereof | |
| CN112974775B (en) | Die, device and method for preparing amorphous alloy pipe | |
| CN100494464C (en) | Plasticized Zr-Cu Al-Ag massive amorphous alloy | |
| CN102605301A (en) | Iron-based block metal glass with high strength and good room temperature plasticity and preparation method thereof | |
| CN107964639B (en) | Carbon and iron-containing zirconium-based block amorphous alloy and preparation process thereof | |
| CN105401105B (en) | High-strength high-plasticity Cu-Zr-Zn amorphous composite and preparation method | |
| CN110153384A (en) | A kind of preparation method of the Fe-based amorphous band of all-metal and amorphous wire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |